Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

Rain-induced debris and mudflow triggering factors assessment in the Santiago cordilleran foothills,Central Chile

Debris and mudflows are some of the main geological hazards in the mountain foothills of the Chilean capital city of Santiago. There, the risk of flows triggered in the basins of ravines that drain the range into the city increases with time due to the city growth. A multivariate statistical study based on the logistic regression method is presented. The model provides equations that allow the computation of combined meteorological triggering factors associated with a probability of rain-induced flow occurrence. Daily rainfall, accumulated rainfall and the snowfall level, traditionally considered as the relevant factors, are analysed for a 25-year period. The results show a strong relevance of the rainfall on the day of the flow event over the other factors. However, the relatively low probabilities returned for some real flow events suggest that the model does not capture all the significant variables and the problem is more complex than as it has been traditionally assumed, and further investigations are needed to develop predictive models of flow triggering.     

Biaxial test simulations using a packing of polygonal particles

The mechanical response of cohesionless granular materials under monotonic loading is studied by performing molecular dynamic simulations. The diversity of shapes of soil grains is modelled by using randomly generated convex polygons as granular particles. Results of the biaxial test obtained for dense and loose media show that samples achieve the same void ratio at large strains independent of their initial density state. This limit state resembles the so‐called critical state of soil mechanics, except for some stress fluctuations, which remain for large deformations. These fluctuations are studied at the micro‐mechanical level, by following the evolution of the co‐ordination number, force chains and the fraction of the sliding contacts of the sample. Copyright © 2007 John Wiley & Sons, Ltd.     

The effect of naturally acidified irrigation water on agricultural volcanic soils. The case of Asembagus, Java, Indonesia

Acid water from the Banyuputih river (pH  3.5) is used for the irrigation of agricultural land in the Asembagus coastal area (East Java, Indonesia), with harmful consequences for rice yields. The river water has an unusual composition which is caused by seepage from the acidic Kawah Ijen crater lake into the river. This unique irrigation setting allows the study of soil acidification in situ. This paper assesses the effects of volcanogenically contaminated irrigation water on the chemical properties of the agricultural soils.The changes in soil properties were evaluated by comparing samples taken from the topsoil and sub-soil (1–3 m depth) from areas irrigated with acid water and areas irrigated with neutral water. The field survey thus resulted in four soil categories. Bulk soil composition, organic matter content, moisture content and particle size distribution were determined. Reactive phases were quantified with the selective extractions 1 M KCl, 0.1 M Na-pyrophosphate and 0.2 M acid ammonium oxalate (AAO).By comparing the four soil categories it is shown that the use of the naturally polluted irrigation water has had a large influence on the chemical composition of the topsoil. The composition of the soil solution has changed over the entire investigated soil profile. Furthermore the acid irrigation water has strongly modified the composition of the reactive phases, extracted as KCl, pyrophosphate, and AAO extractable elements, and also the bulk soil composition has been significantly modified. Overall this has resulted in the net dissolution of some elements and the net precipitation of others. The changes in the reactive phases and bulk soil composition are only apparent in the topsoil (0–20 cm) but not in the deeper soil.     

Geostatistical estimation of chemical contamination in stream sediments: The case study of Vale das Gatas mine (northern Portugal)

Based on an environmental geochemistry case study carried out in the neighbourhood of a W–Sn abandoned mine, the pollution in stream sediments was modelled through a Global Contamination Index. Such an index permits one to summarize the combination of deleterious elements in a single variable, obtained by the projection of samples onto the first axis of a PCASD (Principal Components Analysis of Standardized Data) applied to the entire n × p matrix containing the available concentrations of p = 16 elements in the set of n = 220 collected samples.In order to provide a sound basis for a coherent planning of the remediation process which will be put in operation in the affected area, it is necessary to balance the costs of reclaiming with the probabilities of exceeding the upper limits accepted for concentrations of environmentally harmful elements in sediments. Given these limits, they are back-transformed in the index values, providing a practical threshold between ‘clean’ and ‘contaminated’ samples. On the other hand, the minimum dimension of the cell to be reclaimed is restrained by the selected remediation process to be applied in the affected area. Hence, to meet the constraints of such a remediation process, it is required to estimate the probabilities of exceeding the index threshold in technologically meaningful sub-areas. For this end, the Indicator Block Kriging technique was applied, producing a series of maps where sub-areas to be reclaimed can be spotted for different probability levels. These maps, on which the decision making remediation agency can rely for its cost-benefit analysis, take into account both the spatial structure of ‘clean’ vs. ‘contaminated’ samples and the constraints of the reclaiming process.     

Geological research at the Natural History Museum of Moscow University, 1759-1930 （in Russian）

In 2006, the Moscow publishing house Nauka （Science） published a 246-page book by Zoya A. Bessudnova entitled Geological Research at the Natural History. Museum of Moscow University, 1759-1930 as No. 32 in its series ＂Sketches on the History of Geological Knowledge＇. The author is a geologist and Senior Researcher in the Department for the History of Geology of the Vernadsky State Geological Museum of the Russian Academy of Sciences, and a member of the International Commission on the History of Geological Sci- ences （INHIGEO）.     

Boron incorporation into mullite

Summary Boron-doped mullites were synthesized using aluminium nitrate-nonahydrate, tetraethoxysilane and boric acid in a sol–gel process with subsequent annealing at 950 and 1300 °C for five hours. Two different bulk compositions with constant Al₂O₃ contents (60 and 70 mol%, respectively) and varying SiO₂ plus B₂O₃ contents were investigated. X-ray powder diffraction analyses yielded a linear decrease of the lattice parameters with increasing bulk B₂O₃ content, which was interpreted as to be due to boron incorporation. Related to the increasing boron content, corresponding infrared spectra revealed a slight and continuous shift for most of the absorption bands. These data show that mullite is able to incorporate large amounts of boron into its structure (up to about 20 mol% B₂O₃ depending on the bulk composition of the starting materials). Infrared analyses suggest that boron is incorporated into the mullite structure in form of planar three-fold coordinated BO₃ groups. Author’s address: A. Beran, Institut für Mineralogie und Kristallographie, Universit?t Wien-Geozentrum, Althanstra?e 14, 1090 Wien, Austria     

Analysis of the 2003 Varunawat Landslide,Uttarkashi, India using Earth Observation data

Mass movements such as landslides in mountainous terrains are natural degradation processes and one of the most important landscape-building factors. Varunawat Parbat overlooking Uttarkashi town witnessed a series of landslides on 23 September 2003 and the debris slides and rock falls continued for 2 weeks. This landslide complex was triggered due to the incessant rainfall prior to the event, and its occurrence led to the blockage of the pilgrim route to Gangotri (source of the Ganges river) and evacuation of thousands of people to safer places. Though there was no loss of lives due to timely evacuation, heavy losses to the property were reported. High-resolution stereoscopic earth observation data were acquired after the incidence to study the landslide in detail with emphasis on the cause of the landslide and mode of failure. Areas along the road and below the Varunawat foothill region are mapped for landslide risk. It was found that the foothill region of the Varunawat Parbat was highly disturbed by man-made activities and houses are dangerously located below steep slopes. The potential zones for landslides along with the existing active and old landslides are mapped. These areas are critical and their treatment with priority is required in order to minimise further landslide occurrences.